WO2000043487A1 - Corps moules detergents et nettoyants stables a l'abrasion - Google Patents

Corps moules detergents et nettoyants stables a l'abrasion Download PDF

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Publication number
WO2000043487A1
WO2000043487A1 PCT/EP2000/000202 EP0000202W WO0043487A1 WO 2000043487 A1 WO2000043487 A1 WO 2000043487A1 EP 0000202 W EP0000202 W EP 0000202W WO 0043487 A1 WO0043487 A1 WO 0043487A1
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Prior art keywords
weight
surfactant
granules
detergent
surfactant granules
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PCT/EP2000/000202
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German (de)
English (en)
Inventor
Andreas Lietzmann
Monika Böcker
Heinke Jebens
Hans-Friedrich Kruse
Markus Semrau
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to AU22904/00A priority Critical patent/AU2290400A/en
Publication of WO2000043487A1 publication Critical patent/WO2000043487A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets

Definitions

  • the present invention is in the field of compact molded articles which have washing and cleaning properties.
  • laundry detergent and cleaning agent shaped articles include, for example, detergent shaped articles for washing textiles, detergent shaped articles for machine dishwashing or the cleaning of hard surfaces, bleaching agent shaped articles for use in washing machines or dishwashers, water softening shaped articles or stain remover tablets.
  • the invention relates to detergent tablets which are used for washing textiles in a household washing machine and are referred to briefly as detergent tablets.
  • Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of advantages over powdered detergents: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. Consequently, detergent tablets are also described comprehensively in the patent literature. A problem that occurs again and again when using washing and cleaning active molded articles is the too slow disintegration and dissolving speed of the molded articles under application conditions.
  • EP 687 464 (Allphamed Arzneistoff-Gesellschaft) describes effervescent tablets, consisting of at least one active ingredient or combination of active ingredients, at least one binder, possibly carriers such as flavors, colorants, fragrances, plasticizers, bleaching agents and effervescent additives, propylene glycol or glycerine being the binder. cerin, preferably in amounts of 0.004 to 2.5% by weight. Methods for producing these effervescent tablets are also claimed. According to the statements in this document, a detergent effervescent tablet can also be produced with the teaching according to the invention without the binders used leading to a loss of carbon dioxide in the effervescent additives.
  • EP 711 828 (Unilever) describes detergent tablets which contain surfactant (s), builders (e) and a polymer which acts as a binding and disintegration aid.
  • the binders disclosed in this document are intended to be used at room temperature be solid and be fed to the premix to be ve ⁇ ressing as a melt.
  • Preferred binders are the higher molecular weight polyethylene glycols.
  • the present invention was based on the object of providing moldings which are characterized by short disintegration times given a given hardness and can thus also be metered via the dispensing chamber of household washing machines.
  • the molded body should have increased stability against falling and friction loads, i.e. an improved, i.e. have reduced friability and reduced abrasion behavior.
  • the present invention relates to detergent tablets made from compressed, particulate detergents and cleaning agents which contain a surfactant granulate whose water content is at least 5 percent higher than the water content of the same surfactant granulate at the equilibrium moisture content.
  • the water content of a surfactant granulate (hereinafter used synonymously with the term “water value”) characterizes the percentage by weight of water in the respective granulate, which is at 200 ° C. by means of Karl Fischer titration (KF titration).
  • KF titration Karl Fischer titration
  • the equilibrium moisture content (hereinafter also referred to as equilibrium moisture content) of a granulate is the water content which is obtained on drying in a fluidized bed apparatus with an inlet air temperature of 80 ° C.
  • Both the water content at the equilibrium moisture content and the water content of the moist granules to be used according to the invention relate to the respective granules. If a water content of 10% by weight is determined in the case of a surfactant granulate with equilibrium moisture, 100 grams of this granulate contain 90 grams of constituents which are not titrated as water in the KF tration at 200 ° C. A granulate whose water value is above that at equilibrium moisture content, for example 11% by weight, consequently has only 89 g of constituents per 100 g of granulate, which are not titrated as water in the KF tration at 200 ° C.
  • the above-mentioned value of 5 percent, by which the water content of the surfactant granules according to the invention must be higher than the water value of the same surfactant granules at the equilibrium moisture content is to be understood as a relative indication which is based on the water value at equilibrium moisture content. So it is not 5 percentage points, but 5 percent relative to the water value at equilibrium moisture.
  • the granules to be used according to the invention thus have water contents above 10.5% by weight, based on the moistened granulate.
  • the water value of the surfactant granules used in them is higher than the water value of the same surfactant granules at the equilibrium moisture content.
  • the surfactant granules have a water content which is at least 6 percent, preferably at least 7.5 percent and in particular at least 10 percent higher than the water content of the same surfactant granules at the equilibrium moisture content.
  • the water content of the surfactant granules can vary depending on the composition, with water values above the equilibrium moisture e.g. can be adjusted by adding more water during the granulation process or by using the appropriate drying process (dwell time, supply air temperature). Depending on the composition (which causes the equilibrium moisture content) and on the relative deviation of the water value from the equilibrium moisture content, more or less "moist" granules can be used according to the invention.
  • the surfactant granules each have a water content at the equilibrium moisture content of 5 to 15% by weight, preferably 7.5 to 12.5% by weight and in particular 9 to 11% by weight on the surfactant granules.
  • the water values of the surfactant granules actually used in the detergent tablets according to the invention are at least 5 percent higher than the aforementioned water values of the surfactant granules at the equilibrium moisture content.
  • the above-mentioned numbers are accordingly to be multiplied for the water values of surfactant granules to be used by a factor> 1.05, preferably> 1.06, particularly preferably> 1.075 and in particular> 1.1.
  • detergent tablets according to the invention are preferred, which are characterized in that the surfactant granules used have a water content of 5.25 to 16.5% by weight, preferably 7.9 to 18.15% by weight and in particular 9 , 45 to 12.1% by weight, based in each case on the surfactant granules.
  • the surfactant-free components of a detergent and cleaning product body with a water value above the equilibrium moisture content can also be used.
  • This way too Produce abrasion-resistant molded bodies.
  • the higher water value particularly in the case of components such as enzymes, bleaching agents, bleach activators and foam inhibitors, can lead to a deterioration in the storage stability.
  • the surfactant granule (s) it is therefore preferred if only the surfactant granule (s) have the increased water value.
  • the surfactant granules naturally also contain surfactants. These can come from the groups of anionic, nonionic, cationic or amphoteric surfactants, it also being possible, of course, to use mixtures of the types of surfactants mentioned. Regardless of the type of surfactant used, the surfactant granules in preferred detergent tablets have surfactant contents of 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight, based in each case on the weight of the surfactant granules , on.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Suitable surfactants of the sulfonate type are preferably C 9-13 - alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C 2 - ⁇ 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C] 2-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfate products of saturated fat acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • the alk (en) yl sulfates are the alkali and, in particular, the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C] 0 -C o- Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 2 -C 6 alkyl sulfates and C 12 -C 5 alkyl sulfates and C] 4 -C 5 alkyl sulfates are preferred for washing technology reasons.
  • 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C -21- alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9- n -alcohols with an average of 3.5 mol of ethylene oxide (EO) or C ⁇ 2- ⁇ 8 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • detergent tablets are preferred in which the anionic surfactant content of the surfactant granules is 5 to 45% by weight, preferably 10 to 40% by weight and in particular 15 to 35% by weight, based in each case the weight of the surfactant granules.
  • preferred surfactant granules have a soap content which exceeds 0.2% by weight, based on the total weight of the detergent tablets.
  • the preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent tablets being 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s) , each based on the weight of the detergent tablets
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical has a linear or preferably 2-methyl branching can be or linear and can contain methyl-branched radicals in the mixture, as are usually present in oxo alcohol residues.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • Preferred ethoxylated alcohols include, for example, C 12- ⁇ 4 alcohols containing 3 EO or 4 EO, C 9 n-alcohol with 7 EO, C 13-) 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO , C ⁇ 12- 8 - alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12- 14 - alcohol having 3 EO and C ⁇ ⁇ 2- 8 - alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
  • Alkyl polyglycosides which can be used satisfy the general formula RO (G) 2 , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is Is a symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
  • the surfactant granules can preferably contain alkyl polyglycosides, with APG contents of more than 0.2% by weight, based on the total molded body, being preferred.
  • Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) R ! -OR 2nd
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1-4 alkyl or phenyl radicals being preferred
  • [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • detergent tablets are preferred in which the nonionic surfactant content of the surfactant granules is 1 to 15% by weight, preferably 2.5 to 10% by weight and in particular 5 to 7.5% by weight, in each case based on the weight of the surfactant granules.
  • the surfactant granules In addition to the water and surfactant (s) contained in the surfactant granules in addition to the equilibrium moisture content, the surfactant granules generally contain further ingredients of detergents and cleaning agents. In order to obtain storage-stable and free-flowing surfactant granules, it is preferred if carrier substances are added in the preparation of the surfactant granules, ie the surfactant granules contain builders. Other ingredients of detergents and cleaning agents, in particular so-called small components such as optical brighteners, polymers, defoamers, phosphonates, coloring agents and fragrances, can be part of the surfactant granules. These substances are described below.
  • the surfactant granules can be used in the detergent tablets in varying amounts.
  • Detergent tablets according to the invention which contain the surfactant granules in amounts of 40 to 95% by weight, preferably 45 to 85% by weight and in particular 55 to 75% by weight, in each case based on the weight of the tablet. are preferred.
  • Another object of the present invention is a process for the production of detergent tablets by mixing a surfactant-containing granulate with finely divided preparation components and subsequent molding in a manner known per se, in which the surfactant-containing granulate has a water content of at least 5 percent is higher than the water content of the same surfactant granules at the equilibrium moisture content.
  • the surfactant granules advantageously have a water content of 5.25 to 16.5% by weight, preferably 7.9 to 18.15% by weight and in particular 9.45 to 12.1% by weight , each based on the surfactant granules.
  • the granules containing surfactant are not produced by spray drying, but rather by means of a granulation process.
  • press agglomeration processes can also be used, for example. Method, in which the surfactant-containing granules are produced by granulation, agglomeration, press agglomeration or a combination of these processes are therefore preferred.
  • the granulation can be carried out in a large number of apparatuses customarily used in the detergent and cleaning agent industry. For example, it is possible to use the rounding agents commonly used in pharmacy. In such turntable devices, the residence time of the granules is usually less than 20 seconds.
  • Conventional mixers and mixing granulators are also suitable for granulation. Both high-intensity mixers (“high-shear mixers”) and normal mixers with lower circulation speeds can be used as mixers.
  • Suitable mixers are, for example, Eirich “mixers of the R or RV series (trademark of Maschinenfabrik Gustav Eirich, Hardheim), Schugi ® Flexomix, the Fukae ® FS-G mixer (trademark of Fukae Powtech, Kogyo Co., Japan) Lödige ® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais ® series T or KT (trademark of Drais- Maschinene GmbH, Mannheim).
  • the residence times of the granules in the mixers are in the range of less than 60 seconds, the residence time also being dependent on the speed of rotation of the mixer, with the residence times correspondingly shortening the faster the mixer runs.
  • the residence times of the granules in the mixer / rounder are preferably less than one minute, preferably less than 15 seconds slow-running mixers, for example a Lödige KM, residence times of up to 20 minutes are set, residence times below 10 minutes being preferred because of the economics of the process.
  • the surfactant-containing granules are compressed under pressure and under the action of shear forces, homogenized in the process and then discharged from the apparatus in a shaping manner.
  • the technically most important press agglomeration processes are extrusion, roller compaction, pelleting and tableting.
  • preferred press agglomeration processes used to produce the surfactant-containing granules are extrusion, roller compaction and pelletization.
  • the surfactant-containing granulate is preferably fed continuously to a planetary roller extruder or a 2-screw extruder or 2-screw extruder with co-rotating or counter-rotating screw guide, the housing and the extruder granulating head of which are heated to the predetermined extrusion temperature could be.
  • the premix is compressed, plasticized, and extruded in the form of fine strands through the perforated die plate in the extruder head under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used and finally the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knife.
  • the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.8 to 5 mm and in particular in the range from approximately 1.0 to 3 mm.
  • the length / diameter ratio of the chopped-off primary granules is in the range from about 1: 1 to about 3: 1.
  • extrusion measurements can also be carried out in low-pressure extruders, in the Kahl press or in the extruder.
  • the production process for the surfactant-containing granules is carried out by means of roller compaction.
  • the granules containing surfactant are metered in between two smooth rollers or with depressions of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rollers one keeps smooth, unstructured sliver belts, while by using structured rollers, correspondingly structured slugs or individual pellets can be produced, in which, for example, certain shapes of the later granules or shaped bodies can be specified.
  • the sliver belt is subsequently broken down into smaller pieces by a knocking-off and comminution process and can be processed into granules in this way, which can be further tempered by further known surface treatment methods, in particular in an approximately spherical shape.
  • the preparation of the surfactant-containing granules is carried out by means of pelleting.
  • the granules containing surfactant are applied to a perforated surface and pressed through the holes by means of a pressure-producing body.
  • the surfactant-containing granules are compressed under pressure, plasticized, pressed through a perforated surface in the form of fine strands by means of a rotating roller and finally comminuted to granules with a knock-off device.
  • the most varied configurations of the pressure roller and perforated die are conceivable here.
  • the press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.
  • An apparatus suitable for carrying out the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH).
  • the ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
  • the ring die and the press roller can be driven in the same direction, as a result of which a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
  • the surfactant granulate is then mixed with further preparation components to form a premix, which can then be pressed into detergent tablets.
  • the premix to be treated can contain other ingredients that are common in washing and cleaning agents, in particular from the group of builders, disintegration aids, bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors , Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.
  • the substances mentioned can already be part of the surfactant granules.
  • the washing and cleaning agent shaped bodies according to the invention can contain all of the builders normally used in washing and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - the phosphates.
  • Preferred detergent tablets therefore contain surfactant granules which have a sodium or potassium carbonate content of less than 15% by weight, preferably less than 10% by weight and in particular less than 5% by weight, in each case based on the surfactant granules, exhibit.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + ⁇ 'H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 ⁇ 5 ' yH 2 O are preferred, with ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amo ⁇ h” is also understood to mean “roentgenamo ⁇ h”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments.
  • This is to be integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred .mu.m, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.
  • zeolite of the P and / or X type introduced by the surfactant granules can be inco ⁇ orated into the premix by adding zeolite as a treatment component.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably a type A, P, X or Y zeolite.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • Organic cobuilders that can be used in the detergent tablets according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which, as monomers, contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the monomers contain salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608.
  • An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9).
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • EDTMP hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP, used.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • tablet disintegrants In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times.
  • tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
  • Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the molded article weight.
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and cleaning agent shaped bodies such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H ⁇ 0 O 5 ) n and is formally considered a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.
  • the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated.
  • Detergent tablets which contain disintegrants in granular or optionally granulated form, are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. men.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier available in the present invention.
  • Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
  • a subsequent disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, to granules with an average particle size of 200 ⁇ m.
  • bleaching agents that serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Even when using the bleaching agents it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxyacids, examples of which include Alkyl peroxy acids and the aryl peroxy acids are called.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monophthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidopercapid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid ⁇ and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyocelaic acid diperoxyacid, , 2-Decyldiperoxybutan-l, 4-diacid, N, N-terephthal
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in molded articles for automatic dishwashing.
  • Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,
  • Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium are considered.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • bleach activators can be incorporated into the agents.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines especially tetraacetylethylene diamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid reanhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED tetraacetylethylene diamine
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the shaped bodies according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether, and also the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • the shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-mo ⁇ holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the Mo ⁇ holino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • Dyes and fragrances are added to the detergent tablets according to the invention in order to improve the aesthetic impression of the products and to provide the consumer with a visually and sensorially "typical and unmistakable" product in addition to performance.
  • Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl benzylatepylpropionate, and
  • the ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, oc -Isomethyli
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the dye content of the detergent tablets according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the total formulation.
  • the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • the agents according to the invention can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers, in order not to dye them.
  • the premix Before the particulate premix is pressed into detergent tablets, the premix can be "powdered” with finely divided surface treatment agents. This can be of advantage for the quality and physical properties of both the premix (storage, molding) as well as the finished detergent tablets. Fine powdering agents are in the stand well known in the art, mostly zeolites, silicates or other inorganic salts are used. However, the premix is preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (see Donald W.
  • the or one of the subsequently mixed fine-particle treatment components is a faujasite-type zeolite with particle sizes below 100 ⁇ m, preferably below 100 ⁇ m and in particular below 5 ⁇ m and at least 0.1 2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be treated.
  • the premix to be ve ⁇ re has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular above 700 g / 1, and further contains one or more substances from the group of bleaching agents, bleach activators, Disintegration aids, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.
  • the premix is compacted in a so-called die between two punches to form a solid compact.
  • This process which is briefly referred to as tableting in the following, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, the filling quantity and thus the weight and the shape of the resulting molded body being determined by the position of the lower one Stamp and the shape of the press tool can be determined.
  • the constant dosing is preferably achieved by volumetric dosing of the premix.
  • the upper punch touches the premix and lowers further in the direction of the lower punch. During this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed.
  • the premix particles are also crushed and sintering of the premix occurs at even higher pressures.
  • the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities.
  • the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).
  • Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches.
  • the lower stamp not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down.
  • eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine.
  • the pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disk, the number of die holes being increased accordingly.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
  • Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps.
  • the die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam tracks during the rotation.
  • these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
  • the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix.
  • the pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.
  • Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet.
  • several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling.
  • jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible.
  • Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses are over one million molded articles per hour.
  • Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy NV, Halle (BE / LU).
  • the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.
  • the molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points.
  • the portioned compacts as tablets, in cylinder or cuboid form can be expedient, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred.
  • Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.
  • the spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process.
  • the Detergent Shaped Body easily possible via a dosing aid and preferred in the context of the present invention.
  • Another preferred molded body that can be produced has a plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, broken off and into the Machine can be entered.
  • This principle of the "bar-shaped" shaped body detergent can also be realized in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.
  • the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the moldings that mutually influence one another negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution.
  • the layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).
  • a molded body consists of at least three layers, i.e. two outer and at least one inner layer, at least one of the inner layers containing a peroxy bleaching agent, while in the case of the stacked molded body the two cover layers and in the case of the shell-shaped molded body the outermost layers, however, are free of peroxy bleach.
  • a peroxy bleaching agent i.e. two outer and at least one inner layer, at least one of the inner layers containing a peroxy bleaching agent, while in the case of the stacked molded body the two cover layers and in the case of the shell-shaped molded body the outermost layers, however, are free of peroxy bleach.
  • Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like.
  • the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the melt coating method.
  • the breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to
  • ⁇ stands for diametral fracture stress (DFS) in Pa
  • P is the force in N, which leads to the pressure exerted on the molded body, which causes the molded body to break
  • D is the diameter of the hair dryer in meters and t the height of the molded body.
  • Another object of the present invention is the use of surfactant granules, the water content of which is at least 5 percent higher than the water content of the same surfactant granules at the equilibrium moisture content and which, after mixing with finely divided preparation components, are pressed in a known manner to form detergent tablets for stability - and solubility improvement of detergent tablets.
  • surfactant granules the water content of which is at least 5 percent higher than the water content of the same surfactant granules at the equilibrium moisture content and which, after mixing with finely divided preparation components, are pressed in a known manner to form detergent tablets for stability - and solubility improvement of detergent tablets.
  • a tower powder containing surfactant was produced by spray drying and was used as the basis for a surfactant-containing granulate.
  • the tower powder was granulated with other components (zeolite, FAS granules, nonionic surfactant, polymer) in a 130 liter ploughshare mixer from Lödige.
  • the amounts of the solids and liquids used and the order of addition to the mixer are given in Table 2.
  • a 30 kg granulation batch was divided into 10 kg drying batches in order not to falsify the results due to different wet granules.
  • the granules were sieved with a drying time of 10 minutes (E) or 20 minutes (V) to remove the fine particles ⁇ 0.6 mm and coarse particles> 1.6 mm.
  • the water content of the granules as a function of the drying time was determined by Karl Fischer titration at 200 ° C and is given in Table 3.
  • the surfactant granules E and V were then processed with further components to form a compressible premix, after which the Koring eccentric press led to tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g).
  • the pressure was adjusted so that two series of molded bodies were obtained (El, E2 or VI and V2), which differ in their hardness.
  • the measured values of the tablet hardness and disintegration times are in each case the mean values of a double determination, the individual values varying by type of molded body by a maximum of 2 N or 2 s.
  • Table 1 shows the composition of the spray-dried tower powder.
  • Table 4 shows the composition of the premixes to be pressed (and thus the shaped body).
  • Composition 92% by weight of C 1 - 8 fatty alcohol sulfate
  • the water value of the granulate E according to the invention was thus 11% above the equilibrium moisture.
  • the hardness of the tablets was measured by deforming the tablet until it broke, the force acting on the side surfaces of the tablet and the maximum force which the tablet withstood being determined.
  • the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C.) and the time until the tablet disintegrated completely.
  • the abrasion stability was determined by placing a tablet on a sieve with a mesh size of 1.6 mm. This sieve was then placed in a Retsch analytical sieve machine and stressed with an amplitude of 2 mm over 120 seconds. By weighing the tablet lying on the sieve before and after the stress, the abrasion can be calculated in%.
  • Table 5 The experimental data are shown in Table 5:
  • the molded bodies E according to the invention show a significantly better stability against the frictional load from the vibrating screen.
  • the application properties are consequently further improved by the use of the wetter surfactant granules according to the invention.

Abstract

L'invention concerne des corps moulés détergents et nettoyants qui se distinguent non seulement par une dureté élevée et des temps de décomposition extrêmement courts mais aussi par une stabilité élevée à l'abrasion. Ces corps moulés détergents et nettoyants peuvent être obtenus selon un procédé consistant à incorporer, dans lesdits corps moulés, des granulés de tensioactifs dont la teneur en eau est supérieure d'au moins 5 % à celle du même granulé à l'humidité d'équilibre. La teneur en eau peut être déterminée par titrage KF à 200 °C. L'humidité d'équilibre est atteinte par séchage du granulé à une température d'air d'apport s'élevant à 80 °C, l'humidité de l'air d'apport x étant inférieure à 0,015.
PCT/EP2000/000202 1999-01-22 2000-01-13 Corps moules detergents et nettoyants stables a l'abrasion WO2000043487A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU22904/00A AU2290400A (en) 1999-01-22 2000-01-13 Abrasion-resistant moulded detergent and/or cleaning agent articles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19902425.1 1999-01-22
DE1999102425 DE19902425A1 (de) 1999-01-22 1999-01-22 Abriebstabile Wasch- und Reinigungsmittelformkörper

Publications (1)

Publication Number Publication Date
WO2000043487A1 true WO2000043487A1 (fr) 2000-07-27

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/000202 WO2000043487A1 (fr) 1999-01-22 2000-01-13 Corps moules detergents et nettoyants stables a l'abrasion

Country Status (4)

Country Link
AU (1) AU2290400A (fr)
CA (1) CA2296239A1 (fr)
DE (1) DE19902425A1 (fr)
WO (1) WO2000043487A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0355626A1 (fr) * 1988-08-17 1990-02-28 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation de comprimés détergents à faible teneur en phosphate
EP0711828A2 (fr) * 1994-11-14 1996-05-15 Unilever Plc Compositions détergentes
GB2298867A (en) * 1995-03-11 1996-09-18 Procter & Gamble Detergent compositions in tablet form
DE19709411A1 (de) * 1997-03-07 1998-09-10 Henkel Kgaa Waschmittelformkörper
DE19710254A1 (de) * 1997-03-13 1998-09-17 Henkel Kgaa Wasch- oder reinigungsaktive Formkörper für den Gebrauch im Haushalt
DE19709991A1 (de) * 1997-03-11 1998-09-17 Herzog Stefan In Flüssigkeit zerfallender Preßling

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0355626A1 (fr) * 1988-08-17 1990-02-28 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation de comprimés détergents à faible teneur en phosphate
EP0711828A2 (fr) * 1994-11-14 1996-05-15 Unilever Plc Compositions détergentes
GB2298867A (en) * 1995-03-11 1996-09-18 Procter & Gamble Detergent compositions in tablet form
DE19709411A1 (de) * 1997-03-07 1998-09-10 Henkel Kgaa Waschmittelformkörper
DE19709991A1 (de) * 1997-03-11 1998-09-17 Herzog Stefan In Flüssigkeit zerfallender Preßling
DE19710254A1 (de) * 1997-03-13 1998-09-17 Henkel Kgaa Wasch- oder reinigungsaktive Formkörper für den Gebrauch im Haushalt

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Publication number Publication date
AU2290400A (en) 2000-08-07
CA2296239A1 (fr) 2000-07-22
DE19902425A1 (de) 2000-07-27

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